Antistatic light-sensitive photographic material

ABSTRACT

A multi-layered, light-sensitive silver halide photographic material wherein at least one of its outer layers comprises an ethylene oxide addition polymer of a phenol-formalin condesate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate.

United States Patent Horigome et al.

[ ANTISTATIC LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL [75] Inventors: Koichi Horigome; Kazuyoshi Aoki;

Hisashi Yamaguchi; Hiroshi Horiuchi; Tsuneo Wada, all of Tokyo; Hiroyuki Inokuma, Shiroyama, all of Japan [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 221 Filed: July l3, I972 [2l] Appl. No.: 271,535

[30] Foreign Application Priority Data July 15, l97l Japan 46-52095 [52] US. Cl. 96/87 A, 96/50 Pl, 96/] I4, 96/1 l4.2

[5]] Int. Cl. G03c 1/82, G03c 1/04, G030 1/76 [58] Field of Search 96/87 A, 114.2, 50 PL, 96/114 NOV. 26, 1974 [56] References Cited UNITED STATES PATENTS 2,649,374 8/l953 Richardson 96/87 A 3,551,152 l2/l970 MaCkey et ill. 96/87 A 3,630,740 12/1971 Joseph 61211. 96/87 A Primary E.\aminerCharles Li Bowers, Jr. Attorney, Agent, or Firm-Waters, Roditi, Schwartz & Nissen A multi-layered, light-sensitive silver halide photographic material wherein at least one of its outer lay- I ers comprises an ethylene oxide addition polymer of a 8 Claims, N0 Drawings ANTISTATIC LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL This invention relates to an antistatic light-sensitive photographic material.

When light-sensitive photographic materials are charged with static electricity during the production thereof, many drawbacks result. Substances used as supports for light-sensitive photographic materials are mostly hydrophobic and have such properties as being readily charged with static electricity. Accordingly, the photographic materials are charged with static electricity due to friction with or peeling from other materials during such production steps as, for example, winding, rewinding, application of various layers including lightsensitive layers, and transfer at the time of drying, and the photographic materials coated with light-sensitive layers are sensitized at the time of discharge of the static electricity to form, after development, unevenly sensitized portions called static marks which are caused by the static electricity. Further, when the lightsensitive photographic materials are charged with static electricity at the time of use or treatment thereof, static marks are formed as well, and various drawbacks are brought about due to adhesion of dust or the like to the photographic materials.

The formation of static marks becomes marked with increasing sensitivity of light-sensitive materials. In recent years, light-sensitive materials have been made of greater sensitivity and, in addition, have become increasingly more susceptible to severe mechanical handling problems derived from high speed automatic processing. Accordingly, the tendency of the more recent light-sensitive materials to have static marks therein has become more marked.

In order to prevent light-sensitive materials from static charge, various substances have heretofore been used. Exemplary of such substances which have been used have been those which, in general, are moisture absorptive. There has also been adopted a procedure whereby the light-sensitive materials are rendered conductive by addition of the aforesaid substances to make the accumulation of static electricity difficult. Most of these substances, however, are not only less satisfactory in their applicability to high sensitivity photographic materials, particularly at low humidity, but they also sometimes bring about degradation in antistatic effect, or adhesion troubles at elevated temperatures, and hence cannot always be said to be successfully applicable to lightfsensitive photographic materials.

With the recent development of quick and uniform coating techniques, which have been adopted in order to cope with the rapid increase in the demand for high quality light-sensitive materials, synthetic surface active agents have come to be frequently used as coating aids in the formation of various layers, including lightsensitive layers. Generally, however, most of the synthetic surface active agents which are effective as such coating aids tend to bring about static troubles when used in light-sensitive materials.

Antistatic agents which have heretofore been used can display antistatic effects when applied to lightsensitive materials containing saponin and the like surface active agents of natural origin as coating aids, but most of them cannot display sufficient antistatic effects when applied to light-sensitive materials containing synthetic surface active agents. Accordingly, there has been a definite need for antistatic agents that are capable of displaying sufficient antistatic effects even when applied to light-sensitive materials containing synthetic surface active agents.

An object of the present invention is to provide an effective means for the antistatic treatment of lightsensitive photographic materials, particularly those which are high in sensitivity.

Another object of the invention is to provide an effective means for the antistatic treatment of lightsensitive photographic materials which is effective even when applied to photographic materials containing synthetic surface active agents such as coating aids.

The above objects can be accomplished by incorporating an ethylene oxide addition polymer of a phenolforrnalin condensate into at least one of such outer layers of a light-sensitive photographic material such as a photographic film as the protective layer, overcoating layer, backing layer, antihalation layer and anti-curling layer, or by coating said addition polymer on the surface of at least one of said layers and the film support.

Specifically, the present invention provides a lightsensitive silver halide photographic material having a film support and a light-sensitive silver halide emulsion layer, characterized in that an ethylene oxide addition polymer of a phenol-formalin condensate in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, is present in or on at least one of the outer layers constituting said photographic material. The present invention also specifically provides a multi-layered, light-sensitive silver halide photographic material, comprising at least one of the outer layers constituting the photographic material comprising an ethylene oxide addition polymer of a phenol-formalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate.

The ethylene oxide addition polymer of phenolformalin condensate used in the present invention is obtained by addition polymerizing ethylene oxide with a phenol-formalin condensate of the structural formula,

CH2 I [R1 R2 Jm wherein R and R are individually a hydrogen or halogen atom, or a nitro, carboxyl, alklcarboxy alkoxycarbonyl, alkyl, substituted alkyl or alkoxy group, and m is an integer of l to 100.

Examples of such phenol-formalin condensate are as follows:

4-Methylphenol-formalin resin 2-t-Butylphenol-formalin resin 4-Octylphenol-formalin resin 4-Nonylphenol-formalin resin 4-Tetradecylphenol-formalin resin 2-Octadecylphenol-formalin resin 4-Octadecylphenol-formalin resin 3-Pentadecylphenol-formalin resin 2,4-di-t-Butylphenol-formalin resin 2-Methyl-4-tetradecylphenol-formalin resin 2-Chlorophenol-formalin resin 4-Bromophenol-formalin resin 3-Nitropheno1-formalin resin 4-Carboxyphenol-formalin resin 2-Ch1oro-4-hydroxyethylphenol-formalin resin 2-Chloro-4-chloroethylphenol-formalin resin 2-lodoethyl-4-methoxycarbonylphenol-formalin resin 4-Methoxyphenol-formalin resin 4-Methylcarboxyphenol-formalin resin, and

2-l-lydroxymethyl-3-methylphenol-formalin resin The ethylene oxide addition polymer of the phenolformalin condensate used in the present invention is obtained by addition polymerizing ethylene oxide with one or more of such phenol-formalin condensates as mentioned above. In this case, the amount of ethylene oxide to be addition-polymerized is preferably up to about 30 moles, on the average, per recurring structural unit of the phenol-formalin condensate. If an addition polymer containing more than said amount of ethylene oxide is applied onto the surface of silver halide emulsion layer or is incorporated into layers adjacent thereto, drawbacks result such as the emulsion layer being fogged and the developability of the lightsensitive material being impaired, particularly when development is effected at elevated temperatures in the presence of hydroquinone.

Suitable examples of ethylene oxide addition polymers of phenol-formalin condensates that can be used in the present invention are such compounds as shown below, but it is to be understood that the compounds usable in the present invention are not limited only to these.

Compound (1-1) Polymer obtained by adding 720 moles of ethylene oxide to 4-methylphenol-formalin resin (polymerization degree 90), (an average of 8 moles of ethylene oxide per structural unit of the resin).

Compound (1-2) Polymer obtained by adding 450 moles of ethylene oxide to Z-methylphenol-formalin resin (polymerization degree 30), (an average of 15 moles of ethylene oxide per structural unit of the resin).

Compound (I-3) Polymer obtained by adding 500 moles of ethylene oxide to 4-nonylphenol-forrnalin resin (polymerization degree 50), (an average of 10 moles of ethylene oxide per structural unit of the resin).

Compound (l-4) Polymer obtained by adding 150 moles of ethylene oxide to 2-octylphen0l-formalin resin (polymerization degree 10), (an average of moles of ethylene oxide per structural unit of the resin).

Compound (1-5) Polymer obtained by adding 1,400 moles of ethylene oxide to 4-octadecylphenol-formalin resin (polymerization degree 70), (an average of moles of ethylene oxide per structural unit of the resin).

Compound (1-6) Polymer obtained by adding 750 moles of ethylene oxide to 4-nonylphenol/4-methylphenol-formalin resin [polymerization degree 50 (molar ratio 30/20)], (an average of 15 moles of ethylene oxide per structural unit of the. resin).

Compound (1-7) Polymer obtained by adding 60 moles of ethylene oxide to 4-nonylphenol/2,4-dinony1phenyl-forma1in resin [polymerization degree 3 (molar ratio 1/2)], (an average of 20 moles of ethylene oxide per structural unit of the resin).

Compound (1-8) Polymer obtained by adding 200 moles of ethylene oxide to 2-chlorophenol-formalin resin (polymerization degree 40), (an average of 5 moles of ethylene oxide per structural unit of the resin).

Compound (1-9) Polymer obtained by adding 900 moles of ethylene oxide to 3-nitrophenol-formalin resin (polymerization degree 60), (an average of 15 moles of ethylene oxide per structural unit of the resin).

Compound (I-IO) Polymer obtained by adding 280 moles of ethylene oxide to 2-chloro-4-hydroxyethylphenol/4- methylcarboxyphenol-formalin resin [polymerization degree 40 (molar ratio 2/38)], (an average of 6 moles of ethylene oxide per structural unit of the resin).

Compound (1-11) Polymer obtained by adding 1,360 moles of ethylene oxide to 4-methoxycarbonylphenol-formalin resin (polymerization degree (an average of 17 moles of ethylene oxide per structural unit of the resin).

Compound (1-12) Polymer obtained by adding 600 moles of ethylene oxide to 4-tetradecy1pheno1-formalin resin (polymerization degree 20), (an average of 30 moles of ethylene oxide per structural unit of the resin).

The above-mentioned compounds can be synthesized according to the processes disclosed in Kogyo Kagaku Zasshi (Journal of the Chemical Society of Japan, Industrial Chemistry Section), Vol. 66, 391 (1963), Abura Kagaku (Oil Chemistry), Vol. 12, 625 (1963) and Japanese Patent No. 279,014, but may be synthesized according to other processes. These compounds are viscous, pasty, waxy or semi-solid resins, in general, but are soluble in water and organic solvents such as acetone, alcohol, etc.

In order to be incorporated into the outer layers of a light-sensitive material, the compound used in the present invention can be added to coating liquids used to form said layers, either as is or in the form of a solution in one or more of the aforesaid solvents. In order to apply the compound used in the present invention onto the surface of any of the support and outer layers of a light-sensitive material, a solution of the compound in one or more of the aforesaid solvents-is spray-coated on the said surface, or the support or outer layer is dipped in said solution and then dried.

The compound used in the present invention is an excellent antistatic agent which, even when incorporated into a coating liquid used to form an outer layer of light-sensitive material, does not degrade the coatabil: ity of said coating liquid nor deteriorate the sensitivity, gamma, fog and the like photographic properties of silver halide emulsion layers adjacent to the resulting.

layer incorporated with the compound.

The compound used in the present invention displays its excellent antistatic effect when used in an amount of to 10 mole per m of light-sensitive photographic material. However, the amount of the compound used is not limited to said range, and the optimum amount capable of displaying a desired effect can optionally be selected.

Light-sensitive materials to which the present invention is applicable include all light-sensitive silver halide photographic materials such as ordinary black-white photographic materials, specific black-white photographic materials, color photographic materials, lithographic films and roentogenographic materials (X-ray films).

Further, the compound of the present invention can be effectively applied regardless of the kinds of supports used and the kinds of additives and binders used in silver halide emulsion layers and the like layers constituting the above-mentioned light-sensitive materials. Examples of the supports are polyethylene terephthalate, polycarbonate, polystyrene, polyethylene, polypropylene and cellulose triacetate films, and examples of the binders are gelatin, polyvinyl alcohol, cellulose triacetate and cellulose acetate phthalate.

As coating aids used in forming the layers of lightsensitive photographic materials, there are natural sur face active agents such as saponin and the like and various synthetic surface active agents. Even when any of the above-mentioned surface active agents is used, the compound according to the present invention is able to display a markedly high antistatic effect to effectively prevent the formation of static marks.

Examples of synthetic surface active agents used as coating aids are as follows:

Compound:

(II-3) CioHnOO (RITE:

CsHnOO C OHS OaNa (II-5) 012E250 S OaNa (II-7) 01211250 (CH2CH2O)s S 03K (ll-9) CaHnOCIIQCIICIIQNCIhClhS OaNn OH C1 11 H needless to say, the invention is not limited to these examples.

Example 1 A high sensitivity silver iodobromide gelatin emulsion containing 15 mole percent of silver iodide was subjected to gold sensitization at the time of second ripening. After completion of the second ripening, the emulsion was incorporated with normal amounts of stabilizer, sensitizer, film-hardener and the like additives, and with l g. per liter of the emulsion of the exemplified compound (II-5) as a coating aid. The thus treated emulsion was coated on a polyethylene terephthalate support and then dried to form a silver iodobromide gelatin emulsion layer on the support. The lightsensitive film thus obtained wascut into several specimens.

Separately, an aqueous gelatin solution containing a hardener was charged with l g. per liter of the solution of the exemplified compound (II-3) as a coating aid, and then the resulting protective layer-forming solution was equally divided into two solutions. One of these two solutions was incorporated with 4 g. per liter of the solution of the exemplified compound (1-3) as an antistatic agent, and the other solution was left untreated. Each of the two solutions was coated on one of the aforesaid specimens and then dried.

Light-sensitive film samples prepared in the above manner were individually moistened at a relative humidity (RH) of 20 percent for 10 hours at 25C., rubbed with rubber, and then subjected to ordinary development to observe a state of formation of static marks. As the result, the film having the protective layer incorporated with no antistatic agent showed extremely large numbers of static marks, whereas the film having the protective layer incorporated with the antistatic agent had no static marks.

Further, the surface resistivity of each sample film was measured by the use of two electrodes of 10 cm. in length which had been arranged at a distance of 1 cm. As a result, the surface resistivity at 20C. and 50 percent RH of the film having the protective layer incorporated with no antistatic agent was 6 X 10 (2,

whereas that of the film having the protective layer with the antistatic agent incorporated therein was 3.5 x 10 Q.

Example 2 A high sensitivity silver iodobromide-gelatin emulsion containing 2.0 mole percent of silver iodide was subjected to gold sensitization at the time of second ripening. After completion of the second ripening, the emulsion was subjected to spectral sensitization, and then had incorporated therein normal amounts of stabilizer, hardener and coating aid saponin. The thustreated emulsion was coated on a polyester (polyethylene terephthalate) support and then dried to prepare a light-sensitive film which was cut into several pieces.

Separately, an aqueous gelatin solution containing a hardener was prepared and was equally divided into two solutions. In one of these two solutions 0.5 g/l of saponin was incorporated therein. To the other one was added 0.5 g/l of the exemplified compound (11-14) as coating aid. Each one of the resulting solutions, which were now useful as a protective layer-forming solution, were equally divided into three portions. The first one was used as a blank. Other two were further included, 3 g/l of the exemplified compound (1-6) and 3 g/l of benzyl dimethyl tetradecyl ammonium chloride (control compound A), respectively, as antistatic agent. Thereafter, each of these solutions totalling six in number was coated on each of the cut pieces of the aforesaid light-sensitive film and then dried to form a protective layer thereon.

Sample pieces prepared in the above manner were individually moistened at a relative humidity of percent for 24 hours at C., rubbed with a nylon cloth and then subjected to ordinary development to observe the state of formation of static marks. The results obtained were as set forth in the following table:

As shown in the above table, the exemplified compound (I-6) displayed excellent antistatic effect even when used in combination with any of the natural surface active agents (saponin) and the synthetic surface active agents [exemplified compound (11-14)] used as coating aids, whereas the control compound A, which is a conventional antistatic agent, displayed antistatic effect when used in combination with the natural surface active agent (saponin) but showed no antistatic effect when used in combination with the synthetic antistatic agent [exemplified compound (11-14)].

Example 3 A silver iodobromide color photographic emulsion containing 4 mole percent of silver iodide was subjected to gold sensitization at the time of second ripening. After completion of the second ripening, normal amounts of stabilizer, hardener, saponin as a coating aid, etc., and l-hydroxy-2-N-[6(2,4-di-tertamylphenoxy)butyl]-naphthamide as a cyan coupler, which had been dissolved at an elevated temperature in a mixed solvent comprising di-N-butyl phthalate and ethyl acetate and dispersed in a gelatin solution by use of sodium alkylbenzenesulfonate, were incorporated into the emulsion. The thus-treated emulsion was coated on a cellulose triacetate support and then dried to obtain a light-sensitive film which was then cut into several pieces.

Separately, into an aqueous gelatin solution containing a hardener was incorporated 0.5 g. per liter of the solution of the exemplified compound (11-9) as a coating aid, and then the resulting aqueous gelatin solution was divided into three equal solutions. One of the three solutions was used as a blank and into the remaining two were incorporated 3 g. per liter of the exemplified compound (1-1 and benzyl dimethyl tetradecyl ammonium chloride (control compound A), respectively, as antistatic agents. Thereafter, these three solutions were individually coated on each cut piece of the aforesaid light-sensitive film and then dried.

Sample films pieces all having a protective layer prepared in the above manner were moistened at 20 percent RH for 24 hours at 25C., rubbed with a poly vinyl chloride rod, and then subjected to ordinary color development treatment to observe the state of formation of static marks. As a result, the film having a protective layer with no antistatic agent therein and the film having the protective layer with the control compound A incorporated therein formed extremely large numbers of static marks, whereas the film having a protective layer in which the exemplified compound (1-1) had been incorporated as antistatic agent formed no static marks.

Example 4 A 10 percent aqueous solution of the exemplified compound (1-9) was spray-coated on one side of a cellulose triacetate support and then dried. Subsequently, the same silver iodobromide emulsion as in Example 1 was coated on the other side of the support and then dried.

The surface resistivity at 20C. and 20 percent RH of the film which had been subjected to the abovementioned treatment was 3.5 X 10 0, whereas that of the film which had not been subjected to the abovementioned treatment was 8 X 10 0.

Further, the same static mark test as in Example 1 was effected. As a result, the untreated film showed large numbers of static marks, whereas the treated film showed no static marks.

Example 5 An aqueous gelatin solution containing Malachite Green as an antihalation dye and saponin was incorposolution was coated on the aforesaid emulsion layer rated with the compound Further, the same static mark test as in Example 1 was effected. As a result, the film having the backing and protective layers without the exemplified compound (l-lO) incorporated therein as antistatic agent showed large numbers of static marks, whereas the film having the backing andprotective layers with $513 compound incorporated therein showed no static marks.

The light-sensitive photographic materials of the present invention can not only be effectively prevented from generating static electricity during the production thereof but also can be successfully prevented, even at low humidity, from generating frictional electricity at the time when the photographic materials are packed in cameras or casettes, and the said antistatic effects are not reduced or diminished with time. Further, the photographic materials according to the present invention can be developed, after exposure, without any accumulation of static electricity due to friction with rollers and the like equipment of the developing machine, and the developed photographic materials are not statically charged and hence can be prevented from adhesion of dust and the like.

The antistatic agents used in the present invention display excellent antistatic effects even with lightsensitive materials containing synthetic surface active agents as coating aids, and can successfully prevent the formation of static marks which take place after development of light-sensitive photographic materials that have been statically charged.

What we claim is: v

l. A light-sensitive silver halide photographic material comprising a film support and a light-sensitive silver halide emulsion layer on one side of the film support, an ethylene oxide addition polymer of a phenylformalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, said addition polymer being present in an outer layer on the other side of the film support or in an outer layer on the lightsensitive layer, or in the light-sensitive layer at least at the outer surfacethereof.

2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said ethylene oxide addition polymer of the phenol-formalin condensate is obtained by addition polymerization of ethylene oxide with a phenol-formalin condensate having the following structural formula l ....l l3. i R. L

wherein R and R individually are hydrogen, halogen, a nitro group, a carboxy group, an alkylcarboxy group, an alkoxy carbonyl group, an alkyl group, an alkoxy group or an alkyl group substituted by hydroxy, iodine, or chlorine, and m is an integer of l to 100.

3. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said phenol-formalin condensate is selected from the group consisting of 4-Methylphenol-formalin resin,

2-t-Butylphenol-formalin resin, 4-Octylphenol-formalin resin, 4-Nonylphenol-formalin resin, 4-Tetradecylphenol-formalin resin,

Z-Octadecylphenol-formalin resin,

4-Octadecylphenol-formalin resin,

3-Pentadecylphenol-formalin resin, 2,4-di-t-Butylphenol-fon'nalin resin, 2-Methyl-4-tetradecylphenol-formalin resin, 2-Chlorophenol-formalin resin, 4-Bromophenol-formalin resin,

B-Nitrophenol-formalin resin,

4-Carboxyphenol-formalin resin,

2Chloro-4-hydroxyethylphenol-formalin resin,

2-Chloro-4-chloroethylphenol-formalin resin,

2-Iodoethyl-4-methoxycarbonylphenol-formalin resin,

4.-Methoxyphenol-formalin resin,

4-Methylcarboxyphenol-formalin resin, and

2-Hydroxymethyl-3-methylphenol-formalin resin.

4. A multi-layered, light-sensitive photographic material, comprising a film support, a light-sensitive silver halide emulsion layer on said support, and an outer layer on said film support or on said emulsion layer, an ethylene oxide addition polymer of a phenol-formalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, said addition polymer being present in or on said outer layer.

5. A multi-layered, light-sensitive silver halide photographic material as claimed in claim 4 wherein said 0 outer layer is a protective layer, an overcoat layer, an

anti-halation layer or an anti-curling layer on said emulsion layer.

6. A multi-layered, light-sensitive silver halide photographic material as claimed in claim 5, wherein said outer layer contains and the support is coated with the addition polymer.

7. A multi-layered, light-sensitive silver halide photographic material as claimed in claim 4 wherein said outerlayer is on said support on the side thereof opposite that on which the emulsion layer is disposed.

' 8. A photographic material comprising a film support, a light-sensitive silver halide emulsion layer on said film support, said photographic material having opposite surfaces, and an antistatic material disposed on one of said surfaces or in the substance of the photographic material at said surface, said antistatic material ethylene oxide is not more than 30 moles per structural being an ethylene oxide addition polymer of a phenolunit of the phenol-formalin condensate. formalin condensate, in which the molar proportion of 

1. A LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC MATERIAL COMPRISING A FILM SUPPORT AND A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER ON ONE SIDE OF THE FILM SUPPORT, AN ETHYLENE OXIDE ADDITION POLYMER OF A PHENYL-FORMALIN CONDENSATE, IN WHICH THE MOLAR PROPORTION OF ETHYLENE OXIDE IS NOT MORE THAN 30 MOLES PER STRUCTURAL UNIT OF THE PHENOL-FORMALIN CONDENSATE, SAID ADDITION POLYMER BEING PRESENT IN AN OUTER LAYER ON THE OTHER SIDE OF THE FILM SUPPORT OR IN AN OUTER LAYER ON THE LIGHT-SENSITIVE LAYER, OR IN THE LIGHT-SENSITIVE LAYER AT LEAST AT THE OUTER SURFACE THEREOF.
 2. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said ethylene oxide addition polymer of the phenol-formalin condensate is obtained by addition polymerization of ethylene oxide with a phenol-formalin condensate having the following structural formula
 3. A light-sensitive silver halide photographic material as claimed in claim 1, wherein said phenol-formalin condensate is selected from the group consisting of 4-Methylphenol-formalin resin, 2-t-Butylphenol-formalin resin, 4-Octylphenol-formalin resin, 4-Nonylphenol-formalin resin, 4-Tetradecylphenol-formalin resin, 2-Octadecylphenol-formalin resin, 4-Octadecylphenol-formalin resin, 3-Pentadecylphenol-formalin resin, 2,4-di-t-Butylphenol-formalin resin, 2-Methyl-4-tetradecylphenol-formalin resin, 2-Chlorophenol-formalin resin, 4-Bromophenol-formalin resin, 3-Nitrophenol-formalin resin, 4-Carboxyphenol-formalin resin, 2-Chloro-4-hydroxyethylphenol-formalin resin, 2-Chloro-4-chloroethylphenol-formalin resin, 2-Iodoethyl-4-methoxycarbonylphenol-formalin resin, 4-Methoxyphenol-formalin resin, 4-Methylcarboxyphenol-formalin resin, and 2-Hydroxymethyl-3-methylphenol-formalin resin.
 4. A multi-layered, light-sensitive photographic material, comprising a film support, a light-sensitive silver halide emulsion layer on said support, and an outer layer on said film support or on said emulsion layer, an ethylene oxide addition polymer of a phenol-formalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate, said addition polymer being present in or on said outer layer.
 5. A multi-layered, light-sensitive silver halide photographic material as claimed in claim 4 wherein said outer layer is a protective layer, an overcoat layer, an anti-halation layer or an anti-curling layer on said emulsion layer.
 6. A multi-layered, light-sensitive silver halide photographic material as claimed in claim 5, wherein said outer layer contains and the support is coated with the addition polymer.
 7. A multi-layered, light-sensitive silver halide photographic material as claimed in claim 4 wherein said outer layer is on said support on the side thereof opposite that on which the emulsion layer is disposed.
 8. A photographic material comprising a film support, a light-sensitive silver halide emulsion layer on said film support, said photographic material having opposite surfaces, and an antistatic material disposed on one of said surfaces or in the substance of the photographic material at said surface, said antistatic material being an ethylene oxide addition polymer of a phenol-formalin condensate, in which the molar proportion of ethylene oxide is not more than 30 moles per structural unit of the phenol-formalin condensate. 